WO2017135461A1 - Solid electrolyte and all-solid-state battery - Google Patents

Solid electrolyte and all-solid-state battery Download PDF

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Publication number
WO2017135461A1
WO2017135461A1 PCT/JP2017/004130 JP2017004130W WO2017135461A1 WO 2017135461 A1 WO2017135461 A1 WO 2017135461A1 JP 2017004130 W JP2017004130 W JP 2017004130W WO 2017135461 A1 WO2017135461 A1 WO 2017135461A1
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Prior art keywords
solid electrolyte
content
mol
solid
group
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PCT/JP2017/004130
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French (fr)
Japanese (ja)
Inventor
良平 高野
充 吉岡
武郎 石倉
彰佑 伊藤
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株式会社村田製作所
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Application filed by 株式会社村田製作所 filed Critical 株式会社村田製作所
Priority to CN201780005980.6A priority Critical patent/CN108463916A/en
Priority to EP20176902.3A priority patent/EP3719910A1/en
Priority to EP17747612.4A priority patent/EP3413388B1/en
Priority to JP2017565676A priority patent/JP6593459B2/en
Publication of WO2017135461A1 publication Critical patent/WO2017135461A1/en
Priority to US16/007,008 priority patent/US11444316B2/en

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Definitions

  • the present invention relates to a solid electrolyte and an all-solid battery.
  • Patent Document 1 discloses lithium (Li), lanthanum (La), zirconium (Zr), and oxygen (O) as ceramic materials that have a density and Li conductivity that can be used as solid electrolyte materials.
  • a ceramic material containing aluminum (Al) and having a garnet-type crystal structure is disclosed.
  • the main object of the present invention is to improve the ionic conductivity of the solid electrolyte and to improve the battery characteristics of the all-solid battery.
  • a solid electrolyte having a garnet-type crystal structure containing Li, La, Zr, O and Ga is at least one selected from the group consisting of Al, Mg, Zn and Sc. It has been found that the ionic conductivity of the solid electrolyte can be improved by adding the above element, and the present invention has been achieved.
  • the solid electrolyte according to the present invention is a solid electrolyte having a garnet-type crystal structure.
  • the solid electrolyte according to the present invention includes Li, La, Zr, O, and Ga, and at least one element selected from the group consisting of Al, Mg, Zn, and Sc.
  • the solid electrolyte according to the present invention is a solid electrolyte having a garnet-type crystal structure and containing Li, La, Zr, O, and Ga, and is selected from the group consisting of Al, Mg, Zn, and Sc. And at least one element. Therefore, the solid electrolyte according to the present invention has high ionic conductivity.
  • the Ga content is preferably more than 0 mol% and less than 13.4 mol% with respect to the La content.
  • the total content of at least one element selected from the group consisting of Al, Mg, Zn and Sc is preferably more than 0 mol% and less than 13.4 mol% with respect to the La content.
  • the total of the Ga content and the content of at least one element selected from the group consisting of Al, Mg, Zn and Sc is preferably more than 0.30 mol% and less than 20 mol%.
  • the Ga content is preferably more than 0.66 mol% and less than 6.67 mol% with respect to the La content.
  • the total content of at least one element selected from the group consisting of Al, Mg, Zn and Sc is preferably more than 0 mol% and less than 6.67 mol% with respect to the La content.
  • the total of the Ga content and the content of at least one element selected from the group consisting of Al, Mg, Zn and Sc is preferably more than 0.33 mol% and less than 10 mol%.
  • the content of Zr is preferably 50 mol% or more and 80 mol% or less with respect to the content of La.
  • the Li content is preferably 197 mol% or more and 280 mol% or less with respect to the La content.
  • Solid electrolyte of the present invention have the general formula (Li 7- (3x + ay) Ga x M y) La 3 Zr 2 O 12 (M is Al, Mg, at least one selected from the group consisting of Zn and Sc An element, a is the valence of M, and is preferably a solid electrolyte represented by 0 ⁇ x ⁇ 0.3, 0 ⁇ y ⁇ 0.3, 0.4 ⁇ 3x + ay ⁇ 0.9) .
  • Solid electrolyte of the present invention have the general formula (Li 7- (3x + 3y) Ga x M y) La 3 Zr 2 O 12 (M is Al, 0 ⁇ x ⁇ 0.3,0 ⁇ y ⁇ 0.3 0.1 ⁇ x / y ⁇ 1, 0.6 ⁇ 3x + 3y ⁇ 0.9).
  • the all solid state battery according to the present invention includes a solid electrolyte layer containing the solid electrolyte according to the present invention, a positive electrode joined by sintering to one side of the solid electrolyte layer, and a other side of the solid electrolyte layer joined by sintering.
  • a negative electrode is a solid electrolyte layer containing the solid electrolyte according to the present invention, a positive electrode joined by sintering to one side of the solid electrolyte layer, and a other side of the solid electrolyte layer joined by sintering.
  • the solid electrolyte according to the present invention has high ionic conductivity. Therefore, the solid electrolyte layer containing the solid electrolyte also has high ionic conductivity. Therefore, the all solid state battery according to the present invention is excellent in battery characteristics such as output density.
  • the ionic conductivity of the solid electrolyte can be improved, and the battery characteristics of the all-solid battery can be improved.
  • FIG. 1 is a schematic cross-sectional view of an all solid state battery 1 according to the present embodiment. As shown in FIG. 1, a negative electrode 12, a positive electrode 11, and a solid electrolyte layer 13 are provided.
  • the positive electrode 11 includes positive electrode active material particles.
  • the positive electrode active material particles preferably used include, for example, lithium-containing phosphate compound particles having a NASICON type structure, lithium-containing phosphate compound particles having an olivine type structure, lithium-containing layered oxide particles, and lithium containing a spinel type structure. Examples thereof include oxide particles.
  • Specific examples of the lithium-containing phosphoric acid compound having a NASICON structure that is preferably used include Li 3 V 2 (PO 4 ) 3 and the like.
  • Specific examples of the lithium-containing phosphate compound having an olivine type structure preferably used include Li 3 Fe 2 (PO 4 ) 3 and LiMnPO 4 .
  • lithium-containing layered oxide particles preferably used include LiCoO 2 , LiCo 1/3 Ni 1/3 Mn 1/3 O 2 and the like.
  • lithium-containing oxide having a spinel structure preferably used include LiMn 2 O 4 , LiNi 0.5 Mn 1.5 O 4 , Li 4 Ti 5 O 12 and the like. Only 1 type in these positive electrode active material particles may be used, and multiple types may be mixed and used.
  • the positive electrode 11 may further contain a solid electrolyte.
  • the kind of solid electrolyte contained in the positive electrode 11 is not particularly limited, it is preferable that the same kind of solid electrolyte as the solid electrolyte contained in the solid electrolyte layer 13 is included.
  • the negative electrode 12 includes negative electrode active material particles.
  • the negative electrode active material particles include, for example, MO X (M is at least one selected from the group consisting of Ti, Si, Sn, Cr, Fe, Nb, and Mo. 0.9 ⁇ Compound particles represented by X ⁇ 2.0), graphite-lithium compound particles, lithium metal, lithium alloy particles, lithium-containing phosphate compound particles having a NASICON type structure, lithium-containing phosphate compound particles having an olivine type structure, Examples thereof include lithium-containing oxide particles having a spinel structure.
  • Specific examples of the lithium alloy preferably used include a Li—Al alloy.
  • lithium-containing phosphoric acid compound having a NASICON structure that is preferably used include Li 3 V 2 (PO 4 ) 3 and the like.
  • lithium-containing phosphate compound having an olivine structure that is preferably used include Li 3 Fe 2 (PO 4 ) 3 and the like.
  • lithium-containing oxides having a spinel structure that are preferably used include Li 4 Ti 5 O 12 . Only 1 type in these negative electrode active material particles may be used, and multiple types may be mixed and used.
  • the negative electrode 12 may further contain a solid electrolyte.
  • the kind of solid electrolyte contained in the negative electrode 12 is not particularly limited, it is preferable that the same kind of solid electrolyte as the solid electrolyte contained in the solid electrolyte layer 13 is included.
  • a solid electrolyte layer 13 is disposed between the positive electrode 11 and the negative electrode 12. That is, the positive electrode 11 is disposed on one side of the solid electrolyte layer 13 and the negative electrode 12 is disposed on the other side. Each of the positive electrode 11 and the negative electrode 12 is joined to the solid electrolyte layer 13 by sintering. That is, the positive electrode 11, the solid electrolyte layer 13, and the negative electrode 12 are an integral sintered body.
  • the solid electrolyte contained in the solid electrolyte layer 13 has a garnet-type crystal structure.
  • the garnet-type crystal structure includes not only the crystal structure represented by A 3 B 2 C 3 O 12 but also Li in the C site and also occupied by Li in the interstitial site, That is, A 3 B 2 (C 3 ⁇ x Li x ) Li y O 12, provided that the crystal structure represented by 0 ⁇ x ⁇ 3, 0 ⁇ y ⁇ 6 is included.
  • the solid electrolyte layer 13 has a garnet-type crystal structure, and includes Li, La, Zr, O, and Ga, and at least one element selected from the group consisting of Al, Mg, Zn, and Sc. .
  • the solid electrolyte layer 13 has high ionic conductivity. Therefore, the all solid state battery 1 having the solid electrolyte layer 13 is excellent in battery characteristics such as output density. The reason for this is not clear, but it is considered that at least one selected from the group consisting of Al, Mg, Zn, and Sc is located at the Li site, the Zr site, or the La site, so that high ionic conductivity can be obtained. It is done.
  • At least one selected from the group consisting of Al, Mg, Zn and Sc is mainly located at the Li site, it is considered that the effect of improving the ionic conductivity is the highest, but some elements are at the Zr site or La site. Even when it is located, it is considered that the effect of improving the ionic conductivity is obtained.
  • a part of at least one element selected from the group consisting of Li, La, Zr, O, and Ga and Al, Mg, Zn, and Sc is a composite oxide of Li salt or a constituent element at the grain boundary. May exist as
  • the basic crystal structure of the solid electrolyte contained in the solid electrolyte layer 13 is preferably a garnet type represented by Li 7 La 3 Zr 2 O 12 .
  • the Li: La: Zr: O ratio in this oxide is not necessarily a stoichiometric composition such as 7: 3: 2: 12, and each element may be partially missing.
  • the sum of the Ga content and the content of at least one element selected from the group consisting of Al, Mg, Zn and Sc is more than 0.30 mol%. Preferably less than 20 mol%.
  • the total content of Ga and the content of at least one element selected from the group consisting of Al, Mg, Zn, and Sc is from 3.33 mol%. More than 10 mol% is preferable.
  • the Ga content is preferably more than 0 mol% and less than 13.4 mol% with respect to the La content.
  • the Ga content is preferably more than 0.66 mol% and less than 6.67 mol% with respect to the La content.
  • the total content of at least one element selected from the group consisting of Al, Mg, Zn and Sc is more than 0.30 mol% with respect to the La content. Preferably less than 20 mol%.
  • the content of at least one element selected from the group consisting of Al, Mg, Zn and Sc within the above range, cubic crystals which are high ion conductive phases can be stabilized, and Al, Mg, Zn
  • an impurity layer is formed by reacting Li and La, Zr, and O, which are constituent elements of Sc and a garnet structure, higher ionic conductivity can be realized. From the viewpoint of realizing higher ionic conductivity, the content of at least one element selected from the group consisting of Al, Mg, Zn and Sc is more than 0 mol% with respect to the La content. Less than .67 mol% is preferred.
  • the Zr content is preferably 50 mol% or more and 80 mol% or less with respect to the La content.
  • the Zr content is 60 mol% or more and 70 mol% with respect to the La content. The following is more preferable.
  • the Li content is preferably 197 mol% or more and 280 mol% or less with respect to the La content.
  • the Li content is 203 mol% or more and 220 mol% or less with respect to the La content. It is more preferable that
  • the solid electrolyte contained in the solid electrolyte layer 13 has the general formula (Li 7- (3x + ay) Ga x M y) La 3 Zr 2 O 12 (M is Al, Mg, At least one element selected from the group consisting of Zn and Sc, a is the valence of M, 0 ⁇ x ⁇ 0.3, 0 ⁇ y ⁇ 0.3, 0.4 ⁇ 3x + ay ⁇ 0 .9) is preferably a solid electrolyte represented by the general formula (Li 7- (3x + 3y) Ga x M y ) La 3 Zr 2 O 12 (M is Al, 0 ⁇ x ⁇ 0.3, A solid electrolyte represented by 0 ⁇ y ⁇ 0.3, 0.1 ⁇ x / y ⁇ 1, 0.6 ⁇ 3x + 3y ⁇ 0.9) is more preferable.
  • the reason why the Ga / Al ratio affects the ionic conductivity is not necessarily clear, but is considered as follows.
  • the garnet-type Li site has two sites, an Li1 site and an Li2 site.
  • the Ga and Al added this time are considered to occupy the Li site, but the occupancy to these two sites is presumed to be different between Ga and Al.
  • the occupation balance of the two Li sites changes, and this causes a difference in the conduction path of Li and the site occupation of Li, which is considered to change the conductivity. .
  • x / y and 3x + 3y in the above ranges, it is considered that the Li conduction path advantageous for Li conduction and the site occupation of Li are achieved, and the conductivity is improved.
  • the stoichiometric ratio of Li in the solid electrolyte is preferably 7 ⁇ (3x + ay).
  • it is strictly because of the influence of Li deficiency during sintering and a small amount of impurities generated at the grain boundary. It is difficult to control the amount of Li.
  • it has been found that when the amount of Li contained in the solid electrolyte is within a certain range with respect to the stoichiometric ratio, the ionic conductivity is not significantly reduced.
  • the general formula (Li 7- (3x + ay) Ga x M y ) La 3 Zr 2 O 12 (M is at least one element selected from the group consisting of Al, Mg, Zn and Sc) A is a valence of M, and is preferably a solid electrolyte represented by 0 ⁇ x ⁇ 0.3, 0 ⁇ y ⁇ 0.3, 0.4 ⁇ 3x + ay ⁇ 0.9),
  • the obtained mixed powder is temporarily fired to prepare a temporarily fired body.
  • a solid electrolyte can be obtained by baking the obtained temporary fired body.
  • a raw material of at least one element selected from the group consisting of Ga and Al, Mg, Zn and Sc may be added before sintering. . By doing so, the addition amount of at least one element selected from the group consisting of Ga and Al, Mg, Zn and Sc can be accurately controlled.
  • a paste is prepared by appropriately mixing a solvent, a resin, and the like with the active material particles and the solid electrolyte.
  • the paste is applied on the sheet and dried to form a first green sheet for constituting the positive electrode 11.
  • a second green sheet for forming the negative electrode 12 is formed.
  • a paste is prepared by appropriately mixing a solvent, a resin and the like with the solid electrolyte.
  • the paste is applied and dried to produce a third green sheet for constituting the solid electrolyte layer 13.
  • a laminate is produced by appropriately laminating the first to third green sheets. You may press the produced laminated body. As a preferable pressing method, an isostatic pressing or the like can be mentioned.
  • the all-solid-state battery 1 can be obtained by sintering the laminate.
  • the obtained slurry was dried and calcined at 900 ° C. for 5 hours in a mixed gas of nitrogen gas and air.
  • the solid electrolyte powder coated with butyral resin was pressed at 90 MPa using a tablet molding machine to form a tablet.
  • the obtained solid electrolyte tablet is sufficiently covered with mother powder, sandwiched between two ZrO 2 setters, and then baked at a temperature of 500 ° C. in an oxygen atmosphere to remove the butyral resin, and then an oxygen atmosphere. Then, the temperature was raised to about 1100 ° C. and calcined at 1100 ° C. for 3 hours. Thereafter, the temperature was lowered to obtain a sintered body (solid electrolyte layer) of the solid electrolyte.
  • the bulk density of 4.8g / cm 3 ⁇ 5.0g / cm 3 of about dense sintered body was possible to produce.
  • Example 1 lithium hydroxide monohydrate LiOH.H 2 O, gallium oxide (Ga 2 O 3 ), magnesium oxide (MgO), lanthanum hydroxide (La (OH) 3 ), zirconium oxide (ZrO 2 ) are included.
  • a solid electrolyte layer was produced in the same manner as in Comparative Example 1 except that the raw materials were weighed so as to have the composition shown in Table 1 below.
  • Example 2 As raw materials, lithium hydroxide monohydrate LiOH.H 2 O), gallium oxide (Ga 2 O 3 ), aluminum oxide (Al 2 O 3 ), lanthanum hydroxide (La (OH) 3 ), zirconium oxide (ZrO) A solid electrolyte layer was prepared in the same manner as in Comparative Example 1 except that the raw material containing 2 ) was weighed so as to have the composition shown in Table 1 below.
  • Example 3 lithium hydroxide monohydrate (LiOH.H 2 O), gallium oxide (Ga 2 O 3 ), scandium oxide (Sc 2 O 3 ), lanthanum hydroxide (La (OH) 3 ), zirconium oxide ( A solid electrolyte layer was produced in the same manner as in Comparative Example 1 except that the raw material containing ZrO 2 ) was weighed so as to have the composition shown in Table 1 below.
  • a platinum (Pt) layer serving as a current collector layer was formed on both surfaces of a sintered tablet (solid electrolyte layer) by sputtering, and then sandwiched and fixed by a current collector made of SUS. Thereafter, AC impedance was measured at room temperature (25 ° C.) in the range of 0.1 MHz to 1 MHz ( ⁇ 50 mV) to evaluate ion conductivity. The results are shown in Table 1.
  • FIG. 2 shows a graph (Nyquist plot) showing the measurement results of the AC impedance of the solid electrolyte produced in each of Comparative Example 1 and Example 2.
  • Example 4 As raw materials, lithium hydroxide monohydrate (LiOH.H 2 O), gallium oxide (Ga 2 O 3 ), aluminum oxide (Al 2 O 3 ), lanthanum hydroxide (La (OH) 3 ), zirconium oxide (A solid electrolyte layer was prepared in the same manner as in Comparative Example 1 except that the raw material containing ZrO 2 ) was weighed so as to have the composition shown in Table 2 below, and the ionic conductivity was measured by the above method. The results are shown in Table 2.
  • Example 5 lithium hydroxide monohydrate (LiOH.H 2 O), gallium oxide (Ga 2 O 3 ), aluminum oxide (Al 2 O 3 ), lanthanum hydroxide (La (OH) 3 ), zirconium oxide ( A solid electrolyte layer was prepared in the same manner as in Comparative Example 1 except that the raw material containing ZrO 2 ) was weighed so as to have the composition shown in Table 2 below, and the ionic conductivity was measured by the above method. The results are shown in Table 2.
  • Example 6 lithium hydroxide monohydrate (LiOH.H 2 O), gallium oxide (Ga 2 O 3 ), aluminum oxide (Al 2 O 3 ), lanthanum hydroxide (La (OH) 3 ), zirconium oxide (A solid electrolyte layer was prepared in the same manner as in Comparative Example 1 except that the raw material containing ZrO 2 ) was weighed so as to have the composition shown in Table 2 below, and the ionic conductivity was measured by the above method. The results are shown in Table 2.
  • the ionic conductivity changes when the total content of Ga and Al is constant and the Ga content and the Al content are changed. From the results shown in Table 2, it can be seen that the ionic conductivity can be greatly improved by increasing the Al content to more than 0.66 mol% with respect to the La content. It can also be seen that the conductivity decreases when the Ga content is less than 0.67 mol% with respect to the La content. Accordingly, the Ga content is preferably more than 0.66 mol%. It can be seen that in the region where the content ratio of Ga to Al is more than 0.1 and less than 1, the conductivity becomes almost maximum, which is more preferable.
  • Example 7 As raw materials, lithium hydroxide monohydrate (LiOH.H 2 O), gallium oxide (Ga 2 O 3 ), aluminum oxide (Al 2 O 3 ), lanthanum hydroxide (La (OH) 3 ), zirconium oxide (A solid electrolyte layer was produced in the same manner as in Comparative Example 1 except that the raw materials containing ZrO 2 ) were weighed so as to have the composition shown in Table 3 below, and the ionic conductivity was measured by the above method. The results are shown in Table 3.
  • Example 8 As raw materials, lithium hydroxide monohydrate (LiOH.H 2 O), gallium oxide (Ga 2 O 3 ), aluminum oxide (Al 2 O 3 ), lanthanum hydroxide (La (OH) 3 ), zirconium oxide (A solid electrolyte layer was produced in the same manner as in Comparative Example 1 except that the raw materials containing ZrO 2 ) were weighed so as to have the composition shown in Table 3 below, and the ionic conductivity was measured by the above method. The results are shown in Table 3.
  • Example 9 As raw materials, lithium hydroxide monohydrate (LiOH.H 2 O), gallium oxide (Ga 2 O 3 ), aluminum oxide (Al 2 O 3 ), lanthanum hydroxide (La (OH) 3 ), zirconium oxide (A solid electrolyte layer was produced in the same manner as in Comparative Example 1 except that the raw materials containing ZrO 2 ) were weighed so as to have the composition shown in Table 3 below, and the ionic conductivity was measured by the above method. The results are shown in Table 3.
  • Example 10 As raw materials, lithium hydroxide monohydrate (LiOH.H 2 O), gallium oxide (Ga 2 O 3 ), aluminum oxide (Al 2 O 3 ), lanthanum hydroxide (La (OH) 3 ), zirconium oxide (A solid electrolyte layer was produced in the same manner as in Comparative Example 1 except that the raw materials containing ZrO 2 ) were weighed so as to have the composition shown in Table 3 below, and the ionic conductivity was measured by the above method. The results are shown in Table 3.

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Abstract

To improve the ion conductivity of a solid electrolyte and to improve the battery characteristics of an all-solid-state battery. A solid electrolyte according to the present invention has a garnet crystal structure. This solid electrolyte contains Li, La, Zr, O and Ga, and also contains at least one element selected from the group consisting of Al, Mg, Zn and Sc.

Description

固体電解質及び全固体電池Solid electrolyte and all-solid battery
本発明は、固体電解質及び全固体電池に関する。 The present invention relates to a solid electrolyte and an all-solid battery.
　従来、信頼性及び安全性に優れる二次電池として、全固体電池が知られている。例えば、特許文献１には、固体電解質材料等として使用可能な程度の緻密度やＬｉ伝導率を示すセラミック材料として、リチウム（Ｌｉ）とランタン（Ｌａ）とジルコニウム（Ｚｒ）と酸素（Ｏ）とアルミニウム（Ａｌ）とを含有し、ガーネット型の結晶構造を有するセラミック材料が開示されている。 Conventionally, an all-solid battery is known as a secondary battery excellent in reliability and safety. For example, Patent Document 1 discloses lithium (Li), lanthanum (La), zirconium (Zr), and oxygen (O) as ceramic materials that have a density and Li conductivity that can be used as solid electrolyte materials. A ceramic material containing aluminum (Al) and having a garnet-type crystal structure is disclosed.
特開２０１１－５１８００号公報JP 2011-51800 A
　全固体電池には、固体電解質のイオン伝導度を向上し、全固体電池の電池特性を向上したいという要望がある。 There is a demand for an all-solid-state battery to improve the ionic conductivity of the solid electrolyte and to improve the battery characteristics of the all-solid-state battery.
　本発明の主な目的は、固体電解質のイオン伝導度を向上し、全固体電池の電池特性を向上することにある。 The main object of the present invention is to improve the ionic conductivity of the solid electrolyte and to improve the battery characteristics of the all-solid battery.
　本発明者らは、鋭意研究の結果、Ｌｉ，Ｌａ，Ｚｒ，Ｏ及びＧａを含むガーネット型の結晶構造を有する固体電解質に、Ａｌ，Ｍｇ，Ｚｎ及びＳｃからなる群から選ばれた少なくとも１種の元素を添加することにより固体電解質のイオン伝導度を向上できることを見出し、本発明を成すに至った。 As a result of intensive studies, the inventors have found that a solid electrolyte having a garnet-type crystal structure containing Li, La, Zr, O and Ga is at least one selected from the group consisting of Al, Mg, Zn and Sc. It has been found that the ionic conductivity of the solid electrolyte can be improved by adding the above element, and the present invention has been achieved.
　すなわち、本発明に係る固体電解質は、ガーネット型の結晶構造を有する固体電解質である。本発明に係る固体電解質は、Ｌｉ，Ｌａ，Ｚｒ，Ｏ及びＧａと、Ａｌ，Ｍｇ，Ｚｎ及びＳｃからなる群から選ばれた少なくとも１種の元素とを含む。 That is, the solid electrolyte according to the present invention is a solid electrolyte having a garnet-type crystal structure. The solid electrolyte according to the present invention includes Li, La, Zr, O, and Ga, and at least one element selected from the group consisting of Al, Mg, Zn, and Sc.
　本発明に係る固体電解質は、ガーネット型の結晶構造を有し、かつ、Ｌｉ，Ｌａ，Ｚｒ，Ｏ及びＧａを含む固体電解質であり、かつ、Ａｌ，Ｍｇ，Ｚｎ及びＳｃからなる群から選ばれた少なくとも１種の元素を含む。従って、本発明に係る固体電解質は、高いイオン伝導度を有する。 The solid electrolyte according to the present invention is a solid electrolyte having a garnet-type crystal structure and containing Li, La, Zr, O, and Ga, and is selected from the group consisting of Al, Mg, Zn, and Sc. And at least one element. Therefore, the solid electrolyte according to the present invention has high ionic conductivity.
　本発明に係る固体電解質において、Ｇａの含有量が、Ｌａの含有量に対して０モル％よりも多く１３．４モル％より少ないことが好ましい。Ａｌ，Ｍｇ，Ｚｎ及びＳｃからなる群から選ばれた少なくとも１種の元素の含有量の合計が、Ｌａの含有量に対して０モル％よりも多く１３．４モル％より少ないことが好ましい。Ｇａの含有量と、Ａｌ，Ｍｇ，Ｚｎ及びＳｃからなる群から選ばれた少なくとも１種の元素の含有量との合計が０．３０モル％より多く２０モル％より少ないことが好ましい。 In the solid electrolyte according to the present invention, the Ga content is preferably more than 0 mol% and less than 13.4 mol% with respect to the La content. The total content of at least one element selected from the group consisting of Al, Mg, Zn and Sc is preferably more than 0 mol% and less than 13.4 mol% with respect to the La content. The total of the Ga content and the content of at least one element selected from the group consisting of Al, Mg, Zn and Sc is preferably more than 0.30 mol% and less than 20 mol%.
　本発明に係る固体電解質において、Ｇａの含有量が、Ｌａの含有量に対して０．６６モル％よりも多く６．６７モル％より少ないことが好ましい。Ａｌ，Ｍｇ，Ｚｎ及びＳｃからなる群から選ばれた少なくとも１種の元素の含有量の合計が、Ｌａの含有量に対して０モル％よりも多く６．６７モル％より少ないことが好ましい。Ｇａの含有量と、Ａｌ，Ｍｇ，Ｚｎ及びＳｃからなる群から選ばれた少なくとも１種の元素の含有量との合計が０．３３モル％より多く１０モル％より少ないことが好ましい。 In the solid electrolyte according to the present invention, the Ga content is preferably more than 0.66 mol% and less than 6.67 mol% with respect to the La content. The total content of at least one element selected from the group consisting of Al, Mg, Zn and Sc is preferably more than 0 mol% and less than 6.67 mol% with respect to the La content. The total of the Ga content and the content of at least one element selected from the group consisting of Al, Mg, Zn and Sc is preferably more than 0.33 mol% and less than 10 mol%.
　本発明に係る固体電解質において、Ｚｒの含有量が、Ｌａの含有量に対して５０モル％以上８０モル％以下であることが好ましい。Ｌｉの含有量が、Ｌａの含有量に対して１９７モル％以上２８０モル％以下であることが好ましい。 In the solid electrolyte according to the present invention, the content of Zr is preferably 50 mol% or more and 80 mol% or less with respect to the content of La. The Li content is preferably 197 mol% or more and 280 mol% or less with respect to the La content.
　本発明に係る固体電解質は、一般式（Ｌｉ７－（３ｘ＋ａｙ）ＧａｘＭｙ）Ｌａ３Ｚｒ２Ｏ１２（Ｍは、Ａｌ，Ｍｇ，Ｚｎ及びＳｃからなる群から選ばれた少なくとも１種の元素であり、ａはＭの価数であり、０＜ｘ＜０．３、０＜ｙ＜０．３、０．４＜３ｘ＋ａｙ＜０．９）で表される固体電解質であることが好ましい。 Solid electrolyte of the present invention have the general formula (Li 7- (3x + ay) Ga x M y) La 3 Zr 2 O 12 (M is Al, Mg, at least one selected from the group consisting of Zn and Sc An element, a is the valence of M, and is preferably a solid electrolyte represented by 0 <x <0.3, 0 <y <0.3, 0.4 <3x + ay <0.9) .
　本発明に係る固体電解質は、一般式（Ｌｉ７－（３ｘ＋３ｙ）ＧａｘＭｙ）Ｌａ３Ｚｒ２Ｏ１２（ＭはＡｌであり、０＜ｘ＜０．３、０＜ｙ＜０．３、０．１＜ｘ／ｙ＜１、０．６＜３ｘ＋３ｙ＜０．９）で表される固体電解質であることが好ましい。 Solid electrolyte of the present invention have the general formula (Li 7- (3x + 3y) Ga x M y) La 3 Zr 2 O 12 (M is Al, 0 <x <0.3,0 < y <0.3 0.1 <x / y <1, 0.6 <3x + 3y <0.9).
　本発明に係る全固体電池は、本発明に係る固体電解質を含む固体電解質層と、固体電解質層の一方面に焼結によって接合されている正極と、固体電解質層の他方面に焼結によって接合されている負極とを備える。 The all solid state battery according to the present invention includes a solid electrolyte layer containing the solid electrolyte according to the present invention, a positive electrode joined by sintering to one side of the solid electrolyte layer, and a other side of the solid electrolyte layer joined by sintering. A negative electrode.
　上述のように、本発明に係る固体電解質は、高いイオン伝導度を有する。従って、その固体電解質を含む固体電解質層も高いイオン伝導度を有する。従って、本発明に係る全固体電池は、出力密度などの電池特性に優れている。 As described above, the solid electrolyte according to the present invention has high ionic conductivity. Therefore, the solid electrolyte layer containing the solid electrolyte also has high ionic conductivity. Therefore, the all solid state battery according to the present invention is excellent in battery characteristics such as output density.
　本発明によれば、固体電解質のイオン伝導度を向上し、全固体電池の電池特性を向上することができる。 According to the present invention, the ionic conductivity of the solid electrolyte can be improved, and the battery characteristics of the all-solid battery can be improved.
本発明の一実施形態に係る全固体電池の模式的断面図である。It is typical sectional drawing of the all-solid-state battery which concerns on one Embodiment of this invention. 比較例１及び実施例２のそれぞれにおいて作製した固体電解質の交流インピーダンスの測定結果を示すグラフである。It is a graph which shows the measurement result of the alternating current impedance of the solid electrolyte produced in each of the comparative example 1 and Example 2. FIG.
　以下、本発明を実施した好ましい形態の一例について説明する。但し、下記の実施形態は、単なる例示である。本発明は、下記の実施形態に何ら限定されない。 Hereinafter, an example of a preferable embodiment in which the present invention is implemented will be described. However, the following embodiment is merely an example. The present invention is not limited to the following embodiments.
　また、実施形態等において参照する各図面において、実質的に同一の機能を有する部材は同一の符号で参照することとする。また、実施形態等において参照する図面は、模式的に記載されたものである。図面に描画された物体の寸法の比率などは、現実の物体の寸法の比率などとは異なる場合がある。図面相互間においても、物体の寸法比率等が異なる場合がある。具体的な物体の寸法比率等は、以下の説明を参酌して判断されるべきである。 In each drawing referred to in the embodiment and the like, members having substantially the same function are referred to by the same reference numerals. The drawings referred to in the embodiments and the like are schematically described. A ratio of dimensions of an object drawn in a drawing may be different from a ratio of dimensions of an actual object. The dimensional ratio of the object may be different between the drawings. The specific dimensional ratio of the object should be determined in consideration of the following description.
　図１は、本実施形態に係る全固体電池１の模式的断面図である。図１に示されるように、負極１２と、正極１１と、固体電解質層１３とを備えている。 FIG. 1 is a schematic cross-sectional view of an all solid state battery 1 according to the present embodiment. As shown in FIG. 1, a negative electrode 12, a positive electrode 11, and a solid electrolyte layer 13 are provided.
　正極１１は、正極活物質粒子を含んでいる。好ましく用いられる正極活物質粒子としては、例えば、ナシコン型構造を有するリチウム含有リン酸化合物粒子、オリビン型構造を有するリチウム含有リン酸化合物粒子、リチウム含有層状酸化物粒子、スピネル型構造を有するリチウム含有酸化物粒子等が挙げられる。好ましく用いられるナシコン型構造を有するリチウム含有リン酸化合物の具体例としては、Ｌｉ３Ｖ２（ＰＯ４）３等が挙げられる。好ましく用いられるオリビン型構造を有するリチウム含有リン酸化合物の具体例としては、Ｌｉ３Ｆｅ２（ＰＯ４）３、ＬｉＭｎＰＯ４等が挙げられる。好ましく用いられるリチウム含有層状酸化物粒子の具体例としては、ＬｉＣｏＯ２，ＬｉＣｏ１／３Ｎｉ１／３Ｍｎ１／３Ｏ２等が挙げられる。好ましく用いられるスピネル型構造を有するリチウム含有酸化物の具体例としては、ＬｉＭｎ２Ｏ４，ＬｉＮｉ０．５Ｍｎ１．５Ｏ４、Ｌｉ４Ｔｉ５Ｏ１２等が挙げられる。これらの正極活物質粒子のうちの１種のみを用いてもよいし、複数種類を混合して用いてもよい。 The positive electrode 11 includes positive electrode active material particles. The positive electrode active material particles preferably used include, for example, lithium-containing phosphate compound particles having a NASICON type structure, lithium-containing phosphate compound particles having an olivine type structure, lithium-containing layered oxide particles, and lithium containing a spinel type structure. Examples thereof include oxide particles. Specific examples of the lithium-containing phosphoric acid compound having a NASICON structure that is preferably used include Li 3 V 2 (PO 4 ) 3 and the like. Specific examples of the lithium-containing phosphate compound having an olivine type structure preferably used include Li 3 Fe 2 (PO 4 ) 3 and LiMnPO 4 . Specific examples of the lithium-containing layered oxide particles preferably used include LiCoO 2 , LiCo 1/3 Ni 1/3 Mn 1/3 O 2 and the like. Specific examples of the lithium-containing oxide having a spinel structure preferably used include LiMn 2 O 4 , LiNi 0.5 Mn 1.5 O 4 , Li 4 Ti 5 O 12 and the like. Only 1 type in these positive electrode active material particles may be used, and multiple types may be mixed and used.
　正極１１は、固体電解質をさらに含んでいてもよい。正極１１に含まれる固体電解質の種類は特に限定されないが、固体電解質層１３に含まれる固体電解質と同種の固体電解質を含むことが好ましい。 The positive electrode 11 may further contain a solid electrolyte. Although the kind of solid electrolyte contained in the positive electrode 11 is not particularly limited, it is preferable that the same kind of solid electrolyte as the solid electrolyte contained in the solid electrolyte layer 13 is included.
　負極１２は、負極活物質粒子を含んでいる。好ましく用いられる負極活物質粒子の具体例としては、例えば、ＭＯＸ（Ｍは、Ｔｉ，Ｓｉ，Ｓｎ，Ｃｒ，Ｆｅ，Ｎｂ及びＭｏからなる群より選ばれた少なくとも一種である。０．９≦Ｘ≦２．０）で表される化合物粒子、黒鉛－リチウム化合物粒子、リチウム金属、リチウム合金粒子、ナシコン型構造を有するリチウム含有リン酸化合物粒子、オリビン型構造を有するリチウム含有リン酸化合物粒子、スピネル型構造を有するリチウム含有酸化物粒子等が挙げられる。好ましく用いられるリチウム合金の具体例としては、Ｌｉ－Ａｌ合金等が挙げられる。好ましく用いられるナシコン型構造を有するリチウム含有リン酸化合物の具体例としては、Ｌｉ３Ｖ２（ＰＯ４）３等が挙げられる。好ましく用いられるオリビン型構造を有するリチウム含有リン酸化合物の具体例としては、Ｌｉ３Ｆｅ２（ＰＯ４）３等が挙げられる。好ましく用いられるスピネル型構造を有するリチウム含有酸化物の具体例としては、Ｌｉ４Ｔｉ５Ｏ１２等が挙げられる。これらの負極活物質粒子のうちの１種のみを用いてもよいし、複数種類を混合して用いてもよい。 The negative electrode 12 includes negative electrode active material particles. Specific examples of the negative electrode active material particles preferably used include, for example, MO X (M is at least one selected from the group consisting of Ti, Si, Sn, Cr, Fe, Nb, and Mo. 0.9 ≦ Compound particles represented by X ≦ 2.0), graphite-lithium compound particles, lithium metal, lithium alloy particles, lithium-containing phosphate compound particles having a NASICON type structure, lithium-containing phosphate compound particles having an olivine type structure, Examples thereof include lithium-containing oxide particles having a spinel structure. Specific examples of the lithium alloy preferably used include a Li—Al alloy. Specific examples of the lithium-containing phosphoric acid compound having a NASICON structure that is preferably used include Li 3 V 2 (PO 4 ) 3 and the like. Specific examples of the lithium-containing phosphate compound having an olivine structure that is preferably used include Li 3 Fe 2 (PO 4 ) 3 and the like. Specific examples of lithium-containing oxides having a spinel structure that are preferably used include Li 4 Ti 5 O 12 . Only 1 type in these negative electrode active material particles may be used, and multiple types may be mixed and used.
　負極１２は、固体電解質をさらに含んでいてもよい。負極１２に含まれる固体電解質の種類は特に限定されないが、固体電解質層１３に含まれる固体電解質と同種の固体電解質を含むことが好ましい。 The negative electrode 12 may further contain a solid electrolyte. Although the kind of solid electrolyte contained in the negative electrode 12 is not particularly limited, it is preferable that the same kind of solid electrolyte as the solid electrolyte contained in the solid electrolyte layer 13 is included.
　正極１１と負極１２との間には、固体電解質層１３が配されている。すなわち、固体電解質層１３の一方側に正極１１が配されており、他方側に負極１２が配されている。正極１１及び負極１２のそれぞれは、固体電解質層１３と焼結によって接合されている。すなわち、正極１１、固体電解質層１３及び負極１２は、一体焼結体である。 A solid electrolyte layer 13 is disposed between the positive electrode 11 and the negative electrode 12. That is, the positive electrode 11 is disposed on one side of the solid electrolyte layer 13 and the negative electrode 12 is disposed on the other side. Each of the positive electrode 11 and the negative electrode 12 is joined to the solid electrolyte layer 13 by sintering. That is, the positive electrode 11, the solid electrolyte layer 13, and the negative electrode 12 are an integral sintered body.
　固体電解質層１３に含まれる固体電解質は、ガーネット型の結晶構造を有する。本発明において、ガーネット型の結晶構造は、Ａ３Ｂ２Ｃ３Ｏ１２で表される結晶構造のみならず、ＣサイトにＬｉを含み、かつ格子間サイトにもＬｉが占有しているもの、すなわち、Ａ３Ｂ２（Ｃ３－ｘＬｉｘ）ＬｉｙＯ１２、ただし、０≦ｘ≦３，０≦ｙ≦６で表される結晶構造を含むものとする。 The solid electrolyte contained in the solid electrolyte layer 13 has a garnet-type crystal structure. In the present invention, the garnet-type crystal structure includes not only the crystal structure represented by A 3 B 2 C 3 O 12 but also Li in the C site and also occupied by Li in the interstitial site, That is, A 3 B 2 (C 3−x Li x ) Li y O 12, provided that the crystal structure represented by 0 ≦ x ≦ 3, 0 ≦ y ≦ 6 is included.
　固体電解質層１３は、ガーネット型の結晶構造を有し、かつ、Ｌｉ，Ｌａ，Ｚｒ，Ｏ及びＧａと、Ａｌ，Ｍｇ，Ｚｎ及びＳｃからなる群から選ばれた少なくとも１種の元素とを含む。このため、固体電解質層１３は、高いイオン伝導度を有する。従って、固体電解質層１３を有する全固体電池１は、出力密度などの電池特性に優れている。この理由は定かではないが、Ａｌ，Ｍｇ，Ｚｎ及びＳｃからなる群から選ばれた少なくとも一種が、Ｌｉサイト、Ｚｒサイト又はＬａサイトに位置することにより、高いイオン伝導度が得られるものと考えられる。Ａｌ，Ｍｇ，Ｚｎ及びＳｃからなる群から選ばれた少なくとも一種が主としてＬｉサイトに位置したときにイオン伝導度の向上効果が最も高くなると考えられるが、一部の元素がＺｒサイトやＬａサイトに位置している場合にもイオン伝導度の向上効果が得られるものと考えられる。また、Ｌｉ，Ｌａ，Ｚｒ，Ｏ及びＧａと、Ａｌ，Ｍｇ，Ｚｎ及びＳｃからなる群から選ばれた少なくとも１種の元素の一部は、粒界にＬｉ塩や構成元素との複合酸化物として存在してもよい。 The solid electrolyte layer 13 has a garnet-type crystal structure, and includes Li, La, Zr, O, and Ga, and at least one element selected from the group consisting of Al, Mg, Zn, and Sc. . For this reason, the solid electrolyte layer 13 has high ionic conductivity. Therefore, the all solid state battery 1 having the solid electrolyte layer 13 is excellent in battery characteristics such as output density. The reason for this is not clear, but it is considered that at least one selected from the group consisting of Al, Mg, Zn, and Sc is located at the Li site, the Zr site, or the La site, so that high ionic conductivity can be obtained. It is done. When at least one selected from the group consisting of Al, Mg, Zn and Sc is mainly located at the Li site, it is considered that the effect of improving the ionic conductivity is the highest, but some elements are at the Zr site or La site. Even when it is located, it is considered that the effect of improving the ionic conductivity is obtained. In addition, a part of at least one element selected from the group consisting of Li, La, Zr, O, and Ga and Al, Mg, Zn, and Sc is a composite oxide of Li salt or a constituent element at the grain boundary. May exist as
　固体電解質層１３に含まれる固体電解質の基本結晶構造は、Ｌｉ７Ｌａ３Ｚｒ２Ｏ１２で表されるガーネット型であることが好ましい。但し、この酸化物におけるＬｉ：Ｌａ：Ｚｒ：Ｏ比は必ずしも７：３：２：１２であるように量論組成である必要はなく、各元素が一部欠損していてもよい。 The basic crystal structure of the solid electrolyte contained in the solid electrolyte layer 13 is preferably a garnet type represented by Li 7 La 3 Zr 2 O 12 . However, the Li: La: Zr: O ratio in this oxide is not necessarily a stoichiometric composition such as 7: 3: 2: 12, and each element may be partially missing.
　固体電解質層１３に含まれる固体電解質において、Ｇａの含有量と、Ａｌ，Ｍｇ，Ｚｎ及びＳｃからなる群から選ばれた少なくとも１種の元素の含有量との合計が０．３０モル％より多く２０モル％より少ないことが好ましい。これらの元素の含有量を上記範囲とすることにより、ガーネット型結晶構造における高イオン伝導相である立方晶が好適に保持され、かつ、Ｌｉのイオンパスが好適に形成されるため、より高いイオン伝導度を実現することができる。これらの元素の含有量が低すぎると、ガーネット型結晶構造における高イオン伝導相である立方晶が好適に保持されなくなるため、イオン伝導度が低くなる場合がある。これらの元素の含有量が高すぎると、ＬｉサイトにＧａが存在することで、Ｌｉイオンパスが妨害されることとなり、イオン伝導度が低下する場合がある。より高いイオン伝導度を実現する観点からは、Ｇａの含有量と、Ａｌ，Ｍｇ，Ｚｎ及びＳｃからなる群から選ばれた少なくとも１種の元素の含有量との合計が３．３３モル％より多く１０モル％より少ないことが好ましい。 In the solid electrolyte contained in the solid electrolyte layer 13, the sum of the Ga content and the content of at least one element selected from the group consisting of Al, Mg, Zn and Sc is more than 0.30 mol%. Preferably less than 20 mol%. By setting the content of these elements in the above range, the cubic crystal, which is a high ion conduction phase in the garnet-type crystal structure, is suitably retained, and the Li ion path is suitably formed, so that higher ion conduction is achieved. Degrees can be realized. If the content of these elements is too low, cubic crystals, which are high ion conduction phases in the garnet-type crystal structure, are not suitably retained, so that the ionic conductivity may be lowered. If the content of these elements is too high, the presence of Ga at the Li site will interfere with the Li ion path, which may reduce the ionic conductivity. From the viewpoint of realizing higher ionic conductivity, the total content of Ga and the content of at least one element selected from the group consisting of Al, Mg, Zn, and Sc is from 3.33 mol%. More than 10 mol% is preferable.
　固体電解質層１３に含まれる固体電解質において、Ｇａの含有量が、Ｌａの含有量に対して０モル％よりも多く１３．４モル％より少ないことが好ましい。Ｇａの含有量を上記範囲とすることにより、高イオン伝導相である立方晶を安定化でき、かつ、Ｇａとガーネット型構造を構成元素であるＬｉ，Ｌａ，Ｚｒ，Ｏとが反応して生成する不純物層を低減できるため、より高いイオン伝導度を実現することができる。より高いイオン伝導度を実現する観点からは、Ｇａの含有量が、Ｌａの含有量に対して０．６６モル％よりも多く６．６７モル％より少ないことが好ましい。 In the solid electrolyte contained in the solid electrolyte layer 13, the Ga content is preferably more than 0 mol% and less than 13.4 mol% with respect to the La content. By making the Ga content in the above range, cubic crystals which are high ion conduction phases can be stabilized, and Ga and garnet structure are formed by reaction of Li, La, Zr and O which are constituent elements. Since the impurity layer to be reduced can be reduced, higher ionic conductivity can be realized. From the viewpoint of realizing higher ionic conductivity, the Ga content is preferably more than 0.66 mol% and less than 6.67 mol% with respect to the La content.
　固体電解質層１３に含まれる固体電解質において、Ａｌ，Ｍｇ，Ｚｎ及びＳｃからなる群から選ばれた少なくとも１種の元素の含有量の合計が、Ｌａの含有量に対し０．３０モル％より多く２０モル％より少ないことが好ましい。Ａｌ，Ｍｇ，Ｚｎ及びＳｃからなる群から選ばれた少なくとも１種の元素の含有量を上記範囲とすることにより、高イオン伝導相である立方晶を安定化でき、かつ、Ａｌ，Ｍｇ、Ｚｎ及びＳｃとガーネット型構造を構成元素であるＬｉ，Ｌａ，Ｚｒ，Ｏとが反応して生成する不純物層が生成するため、より高いイオン伝導度を実現することができる。より高いイオン伝導度を実現する観点からは、Ａｌ，Ｍｇ，Ｚｎ及びＳｃからなる群から選ばれた少なくとも１種の元素の含有量が、Ｌａの含有量に対して０モル％よりも多く６．６７モル％より少ないことが好ましい。 In the solid electrolyte contained in the solid electrolyte layer 13, the total content of at least one element selected from the group consisting of Al, Mg, Zn and Sc is more than 0.30 mol% with respect to the La content. Preferably less than 20 mol%. By setting the content of at least one element selected from the group consisting of Al, Mg, Zn and Sc within the above range, cubic crystals which are high ion conductive phases can be stabilized, and Al, Mg, Zn In addition, since an impurity layer is formed by reacting Li and La, Zr, and O, which are constituent elements of Sc and a garnet structure, higher ionic conductivity can be realized. From the viewpoint of realizing higher ionic conductivity, the content of at least one element selected from the group consisting of Al, Mg, Zn and Sc is more than 0 mol% with respect to the La content. Less than .67 mol% is preferred.
　固体電解質層１３に含まれる固体電解質において、Ｚｒの含有量が、Ｌａの含有量に対し５０モル％以上８０モル％以下であることが好ましい。Ｚｒの含有量を上記範囲とすることにより、ガーネット型構造をとりやすくなり、より高いイオン伝導度を実現する観点から、Ｚｒの含有量は、Ｌａの含有量に対し６０モル％以上７０モル％以下であることがより好ましい。 In the solid electrolyte contained in the solid electrolyte layer 13, the Zr content is preferably 50 mol% or more and 80 mol% or less with respect to the La content. By making the Zr content in the above range, it becomes easy to take a garnet structure, and from the viewpoint of realizing higher ionic conductivity, the Zr content is 60 mol% or more and 70 mol% with respect to the La content. The following is more preferable.
　固体電解質層１３に含まれる固体電解質において、Ｌｉの含有量が、Ｌａの含有量に対し１９７モル％以上２８０モル％以下である、ことが好ましい。また、ＬｉｘＬａ３Ｚｒ２Ｏ１２である場合は、５．９≦ｘ≦８．４であることが好ましい。Ｌｉの含有量を上記範囲とすることにより、ガーネット型構造をとりやすくなり、より高いイオン伝導度実現する観点から、Ｌｉの含有量は、Ｌａの含有量に対し２０３モル％以上２２０モル％以下であることがより好ましい。 In the solid electrolyte contained in the solid electrolyte layer 13, the Li content is preferably 197 mol% or more and 280 mol% or less with respect to the La content. In the case of Li x La 3 Zr 2 O 12 , it is preferable that 5.9 ≦ x ≦ 8.4. By making the Li content in the above range, it becomes easy to take a garnet structure, and from the viewpoint of realizing higher ionic conductivity, the Li content is 203 mol% or more and 220 mol% or less with respect to the La content. It is more preferable that
　さらに高い伝導度を実現する観点からは、固体電解質層１３に含まれる固体電解質は、一般式（Ｌｉ７－（３ｘ＋ａｙ）ＧａｘＭｙ）Ｌａ３Ｚｒ２Ｏ１２（Ｍは、Ａｌ，Ｍｇ，Ｚｎ及びＳｃからなる群から選ばれた少なくとも１種の元素であり、ａはＭの価数であり、０＜ｘ＜０．３、０＜ｙ＜０．３、０．４＜３ｘ＋ａｙ＜０．９）で表される固体電解質であることが好ましく、一般式（Ｌｉ７－（３ｘ＋３ｙ）ＧａｘＭｙ）Ｌａ３Ｚｒ２Ｏ１２（ＭはＡｌであり、０＜ｘ＜０．３、０＜ｙ＜０．３、０．１＜ｘ／ｙ＜１、０．６＜３ｘ＋３ｙ＜０．９）で表される固体電解質であることがより好ましい。 From the viewpoint of realizing a higher conductivity, the solid electrolyte contained in the solid electrolyte layer 13 has the general formula (Li 7- (3x + ay) Ga x M y) La 3 Zr 2 O 12 (M is Al, Mg, At least one element selected from the group consisting of Zn and Sc, a is the valence of M, 0 <x <0.3, 0 <y <0.3, 0.4 <3x + ay <0 .9) is preferably a solid electrolyte represented by the general formula (Li 7- (3x + 3y) Ga x M y ) La 3 Zr 2 O 12 (M is Al, 0 <x <0.3, A solid electrolyte represented by 0 <y <0.3, 0.1 <x / y <1, 0.6 <3x + 3y <0.9) is more preferable.
　Ｇａ／Ａｌ比がイオン伝導度に影響を与える理由は必ずしも明らかではないが、以下のように考えられる。ガーネット型のＬｉサイトには２つのサイト、Ｌｉ１サイト、Ｌｉ２サイトが存在する。今回添加したＧａ，ＡｌはＬｉサイトを占有しているものと考えられるが、これら２つのサイトへの占有性はＧａ、Ａｌで異なっていると推定される。Ｇａ、Ａｌの添加比が変化すると、２つのＬｉサイトの占有バランスが変化し、これがＬｉの伝導パスや、Ｌｉのサイト占有性に差異が生じさせることで、伝導度が変化するものと考えられる。ｘ／ｙ及び３ｘ＋３ｙを上記範囲とすることにより、Ｌｉ伝導に有利なＬｉの伝導パスや、Ｌｉのサイト占有性が達成され、伝導度が向上したものと考えられる。 The reason why the Ga / Al ratio affects the ionic conductivity is not necessarily clear, but is considered as follows. The garnet-type Li site has two sites, an Li1 site and an Li2 site. The Ga and Al added this time are considered to occupy the Li site, but the occupancy to these two sites is presumed to be different between Ga and Al. When the addition ratio of Ga and Al changes, the occupation balance of the two Li sites changes, and this causes a difference in the conduction path of Li and the site occupation of Li, which is considered to change the conductivity. . By setting x / y and 3x + 3y in the above ranges, it is considered that the Li conduction path advantageous for Li conduction and the site occupation of Li are achieved, and the conductivity is improved.
　なお、固体電解質においてＬｉの量論比は、７－（３ｘ＋ａｙ）であることが好ましいが、ガーネット型化合物では、焼結時におけるＬｉ欠損や、粒界に生成する微量の不純物の影響から、厳密にＬｉ量を制御するのは困難である。本発明者らが鋭意研究した結果、固体電解質に含まれるＬｉ量が量論比に対して、ある一定の範囲内にある場合、イオン伝導度が大幅に低下しないことが見出された。具体的には、固体電解質においてＬｉの量論比７－（３ｘ＋ａｙ）に対して、±１０ｍｏｌ％程度の範囲にあることが好ましく、さらに±３ｍｏｌ％程度であることがさらに好ましい。従って、本発明においては、一般式（Ｌｉ７－（３ｘ＋ａｙ）ＧａｘＭｙ）Ｌａ３Ｚｒ２Ｏ１２（Ｍは、Ａｌ，Ｍｇ，Ｚｎ及びＳｃからなる群から選ばれた少なくとも１種の元素であり、ａはＭの価数であり、０＜ｘ＜０．３、０＜ｙ＜０．３、０．４＜３ｘ＋ａｙ＜０．９）で表される固体電解質であることが好ましく、一般式（Ｌｉ７－（３ｘ＋３ｙ）ＧａｘＭｙ）Ｌａ３Ｚｒ２Ｏ１２（ＭはＡｌであり、０＜ｘ＜０．３、０＜ｙ＜０．３、０．１＜ｘ／ｙ＜１、０．６＜３ｘ＋３ｙ＜０．９）で表される固体電解質には、Ｌｉの量論比が７－（３ｘ＋ａｙ）に対して、±１０ｍｏｌ％程度の範囲にある固体電解質が含まれるものとする。 The stoichiometric ratio of Li in the solid electrolyte is preferably 7− (3x + ay). However, in the case of a garnet type compound, it is strictly because of the influence of Li deficiency during sintering and a small amount of impurities generated at the grain boundary. It is difficult to control the amount of Li. As a result of intensive studies by the present inventors, it has been found that when the amount of Li contained in the solid electrolyte is within a certain range with respect to the stoichiometric ratio, the ionic conductivity is not significantly reduced. Specifically, it is preferably in the range of about ± 10 mol%, more preferably about ± 3 mol% with respect to the Li stoichiometric ratio of 7− (3x + ay) in the solid electrolyte. Therefore, in the present invention, the general formula (Li 7- (3x + ay) Ga x M y ) La 3 Zr 2 O 12 (M is at least one element selected from the group consisting of Al, Mg, Zn and Sc) A is a valence of M, and is preferably a solid electrolyte represented by 0 <x <0.3, 0 <y <0.3, 0.4 <3x + ay <0.9), General formula (Li 7- (3x + 3y) Ga x M y ) La 3 Zr 2 O 12 (M is Al, 0 <x <0.3, 0 <y <0.3, 0.1 <x / y The solid electrolyte represented by <1, 0.6 <3x + 3y <0.9) includes a solid electrolyte having a Li stoichiometric ratio in the range of about ± 10 mol% with respect to 7− (3x + ay). Shall.
　（固体電解質の製造方法）
　次に、固体電解質の製造方法の一例について説明する。 (Method for producing solid electrolyte)
Next, an example of a method for producing a solid electrolyte will be described.
　まず、Ｌｉ源となる原料、Ｚｒ源となる原料、Ｌａ源となる原料、およびＧａ及びＡｌ，Ｍｇ，Ｚｎ及びＳｃからなる群から選ばれた少なくとも１種の元素の原料を、所望の割合で秤量し、混合する。得られた混合粉末を仮焼成することにより、仮焼成体を作製する。得られた仮焼成体を焼成することにより固体電解質を得ることができる。なお、まず、ガーネット型の結晶相を作製した後に、焼結前の段階で、Ｇａ及びＡｌ，Ｍｇ，Ｚｎ及びＳｃからなる群から選ばれた少なくとも１種の元素の原料を添加してもよい。そうすることにより、Ｇａ及びＡｌ，Ｍｇ，Ｚｎ及びＳｃからなる群から選ばれた少なくとも１種の元素の添加量を正確に制御することができる。 First, a raw material to be a Li source, a raw material to be a Zr source, a raw material to be a La source, and a raw material of at least one element selected from the group consisting of Ga, Al, Mg, Zn and Sc, in a desired ratio Weigh and mix. The obtained mixed powder is temporarily fired to prepare a temporarily fired body. A solid electrolyte can be obtained by baking the obtained temporary fired body. First, after preparing a garnet-type crystal phase, a raw material of at least one element selected from the group consisting of Ga and Al, Mg, Zn and Sc may be added before sintering. . By doing so, the addition amount of at least one element selected from the group consisting of Ga and Al, Mg, Zn and Sc can be accurately controlled.
　（全固体電池１の製造方法）
　次に、全固体電池１の製造方法の一例について説明する。 (Manufacturing method of all solid state battery 1)
Next, an example of a method for manufacturing the all solid state battery 1 will be described.
　まず、活物質粒子と固体電解質とに対して、溶剤、樹脂等を適宜混合することにより、ペーストを調製する。そのペーストをシートの上に塗布し、乾燥させることにより正極１１を構成するための第１のグリーンシートを形成する。同様に、負極１２を構成するための第２のグリーンシートを形成する。 First, a paste is prepared by appropriately mixing a solvent, a resin, and the like with the active material particles and the solid electrolyte. The paste is applied on the sheet and dried to form a first green sheet for constituting the positive electrode 11. Similarly, a second green sheet for forming the negative electrode 12 is formed.
　固体電解質に対して、溶剤、樹脂等を適宜混合することにより、ペーストを調製する。そのペーストを塗布し、乾燥させることにより、固体電解質層１３を構成するための第３のグリーンシートを作製する。 A paste is prepared by appropriately mixing a solvent, a resin and the like with the solid electrolyte. The paste is applied and dried to produce a third green sheet for constituting the solid electrolyte layer 13.
　次に、第１～第３のグリーンシートを適宜積層することにより積層体を作製する。作製した積層体をプレスしてもよい。好ましいプレス方法としては、静水圧プレス等が挙げられる。 Next, a laminate is produced by appropriately laminating the first to third green sheets. You may press the produced laminated body. As a preferable pressing method, an isostatic pressing or the like can be mentioned.
　その後、積層体を焼結することにより全固体電池１を得ることができる。 Thereafter, the all-solid-state battery 1 can be obtained by sintering the laminate.
　以下、本発明について、具体的な実施例に基づいて、さらに詳細に説明するが、本発明は以下の実施例に何ら限定されるものではなく、その要旨を変更しない範囲において適宜変更して実施することが可能である。 Hereinafter, the present invention will be described in more detail on the basis of specific examples. However, the present invention is not limited to the following examples, and may be appropriately modified and implemented without departing from the scope of the present invention. Is possible.
　（比較例１）
　水酸化リチウム一水和物（ＬｉＯＨ・Ｈ２Ｏ）、酸化アルミニウム（Ａｌ２Ｏ３）、水酸化ランタン（Ｌａ（ＯＨ）３）、酸化ジルコニウム（ＺｒＯ２）を含む原料を下記の表１に示す組成となるように秤量した。次に、水を添加し、１００ｍｌのポリエチレン製ポリポットに封入して、ポット架上で１５０ｒｐｍ、１６時間回転させ、原料を混合した。なお、また、Ｌｉ源である水酸化リチウム一水和物ＬｉＯＨ・Ｈ２Ｏは焼結時のＬｉ欠損を考慮し、狙い組成に対し、５質量％過剰に仕込んだ。 (Comparative Example 1)
The raw materials containing lithium hydroxide monohydrate (LiOH.H 2 O), aluminum oxide (Al 2 O 3 ), lanthanum hydroxide (La (OH) 3 ) and zirconium oxide (ZrO 2 ) are shown in Table 1 below. It weighed so that it might become the composition shown. Next, water was added, sealed in a 100 ml polyethylene polypot, and rotated on a pot rack at 150 rpm for 16 hours to mix the raw materials. In addition, lithium hydroxide monohydrate LiOH.H 2 O as a Li source was charged in excess of 5% by mass with respect to the target composition in consideration of Li deficiency during sintering.
　次に、得られたスラリーを乾燥させた後に、窒素ガスと空気との混合ガス中で９００℃で５時間仮焼した。 Next, the obtained slurry was dried and calcined at 900 ° C. for 5 hours in a mixed gas of nitrogen gas and air.
　次に、得られた仮焼成物にトルエン－アセトンの混合溶媒を添加し、遊星ボールミルにて６時間粉砕し、固体電解質を得た。 Next, a toluene-acetone mixed solvent was added to the obtained calcined product, and the mixture was pulverized with a planetary ball mill for 6 hours to obtain a solid electrolyte.
　次に、固体電解質、ブチラール樹脂、アルコールを、２００：１５：１４０の質量比率で混合した後、８０℃のホットプレート上でアルコールを除去し、バインダーとなるブチラール樹脂で被覆された固体電解質粉末を得た。 Next, after the solid electrolyte, butyral resin, and alcohol are mixed at a mass ratio of 200: 15: 140, the alcohol is removed on a hot plate at 80 ° C., and the solid electrolyte powder coated with the butyral resin as a binder is obtained. Obtained.
　次に、ブチラール樹脂で被覆された固体電解質粉末を錠剤成型機を用いて９０ＭＰａでプレスしてタブレット状に成型した。得られた固体電解質のタブレットを、マザーパウダーで十分に覆い、２枚のＺｒＯ２セッターで挟持した後、酸素雰囲気下、５００℃の温度で焼成することにより、ブチラール樹脂を除去した後、酸素雰囲気下で約１１００℃まで昇温し、１１００℃で３時間焼成した。その後、降温することで固体電解質の焼結体（固体電解質層）を得た。以上の手法によって固体電解質の焼結体を作製することで、かさ密度が４．８ｇ／ｃｍ３～５．０ｇ／ｃｍ３程度の緻密な焼結体が作製可能であった。 Next, the solid electrolyte powder coated with butyral resin was pressed at 90 MPa using a tablet molding machine to form a tablet. The obtained solid electrolyte tablet is sufficiently covered with mother powder, sandwiched between two ZrO 2 setters, and then baked at a temperature of 500 ° C. in an oxygen atmosphere to remove the butyral resin, and then an oxygen atmosphere. Then, the temperature was raised to about 1100 ° C. and calcined at 1100 ° C. for 3 hours. Thereafter, the temperature was lowered to obtain a sintered body (solid electrolyte layer) of the solid electrolyte. By making a sintered body of the solid electrolyte by the above method, the bulk density of 4.8g / cm 3 ~ 5.0g / cm 3 of about dense sintered body was possible to produce.
　（実施例１）
　原料として、水酸化リチウム一水和物ＬｉＯＨ・Ｈ２Ｏ、酸化ガリウム（Ｇａ２Ｏ３）、酸化マグネシウム（ＭｇＯ）、水酸化ランタン（Ｌａ（ＯＨ）３）、酸化ジルコニウム（ＺｒＯ２）を含む原料を下記の表１に示す組成となるように秤量したこと以外は、比較例１と同様にして固体電解質層を作製した。 Example 1
As raw materials, lithium hydroxide monohydrate LiOH.H 2 O, gallium oxide (Ga 2 O 3 ), magnesium oxide (MgO), lanthanum hydroxide (La (OH) 3 ), zirconium oxide (ZrO 2 ) are included. A solid electrolyte layer was produced in the same manner as in Comparative Example 1 except that the raw materials were weighed so as to have the composition shown in Table 1 below.
　（実施例２）
　原料として、水酸化リチウム一水和物ＬｉＯＨ・Ｈ２Ｏ）、酸化ガリウム（Ｇａ２Ｏ３）、酸化アルミニウム（Ａｌ２Ｏ３）、水酸化ランタン（Ｌａ（ＯＨ）３）、酸化ジルコニウム（ＺｒＯ２）を含む原料を下記の表１に示す組成となるように秤量したこと以外は、比較例１と同様にして固体電解質層を作製した。 (Example 2)
As raw materials, lithium hydroxide monohydrate LiOH.H 2 O), gallium oxide (Ga 2 O 3 ), aluminum oxide (Al 2 O 3 ), lanthanum hydroxide (La (OH) 3 ), zirconium oxide (ZrO) A solid electrolyte layer was prepared in the same manner as in Comparative Example 1 except that the raw material containing 2 ) was weighed so as to have the composition shown in Table 1 below.
　（実施例３）
　原料として、水酸化リチウム一水和物（ＬｉＯＨ・Ｈ２Ｏ）、酸化ガリウム（Ｇａ２Ｏ３）、酸化スカンジウム（Ｓｃ２Ｏ３）、水酸化ランタン（Ｌａ（ＯＨ）３）、酸化ジルコニウム（ＺｒＯ２）を含む原料を下記の表１に示す組成となるように秤量したこと以外は、比較例１と同様にして固体電解質層を作製した。 (Example 3)
As raw materials, lithium hydroxide monohydrate (LiOH.H 2 O), gallium oxide (Ga 2 O 3 ), scandium oxide (Sc 2 O 3 ), lanthanum hydroxide (La (OH) 3 ), zirconium oxide ( A solid electrolyte layer was produced in the same manner as in Comparative Example 1 except that the raw material containing ZrO 2 ) was weighed so as to have the composition shown in Table 1 below.
　（固体電解質層のイオン伝導度の測定）
　比較例及び実施例１～３のそれぞれにおいて作製した固体電解質層のイオン伝導度を以下の要領で測定した。 (Measurement of ionic conductivity of solid electrolyte layer)
The ionic conductivity of the solid electrolyte layer produced in each of the comparative example and Examples 1 to 3 was measured as follows.
　まず、焼結タブレット（固体電解質層）の両面にスパッタリングによって、集電体層となる白金（Ｐｔ）層を形成した後、ＳＵＳ製の集電体で挟持し、固定した。その後、０．１ＭＨｚ～１ＭＨｚ（±５０ｍＶ）の範囲で室温（２５℃）にて交流インピーダンス測定を行い、イオン伝導度を評価した。結果を表１に示す。 First, a platinum (Pt) layer serving as a current collector layer was formed on both surfaces of a sintered tablet (solid electrolyte layer) by sputtering, and then sandwiched and fixed by a current collector made of SUS. Thereafter, AC impedance was measured at room temperature (25 ° C.) in the range of 0.1 MHz to 1 MHz (± 50 mV) to evaluate ion conductivity. The results are shown in Table 1.
　また、図２に、比較例１及び実施例２のそれぞれにおいて作製した固体電解質の交流インピーダンスの測定結果を示すグラフ（ナイキストプロット）を示す。 FIG. 2 shows a graph (Nyquist plot) showing the measurement results of the AC impedance of the solid electrolyte produced in each of Comparative Example 1 and Example 2.
Figure JPOXMLDOC01-appb-T000001
  　表１に示す結果から、Ｇａと、Ａｌ，Ｍｇ又はＳｃとを含有させることにより、イオン伝導度を高めることができることが分かる。なお、Ｍｇと同じ価数で、同程度のイオン半径を有するＺｎを含有させた場合にも同様の効果が期待できる。
Figure JPOXMLDOC01-appb-T000001
 From the results shown in Table 1, it can be seen that the ionic conductivity can be increased by containing Ga and Al, Mg or Sc. In addition, the same effect can be expected when Zn having the same valence as Mg and the same ionic radius is contained.
　（実施例４）
　原料として、水酸化リチウム一水和物（ＬｉＯＨ・Ｈ２Ｏ）、酸化ガリウム（Ｇａ２Ｏ３）、酸化アルミニウム（Ａｌ２Ｏ３）、水酸化ランタン（Ｌａ（ＯＨ）３）、酸化ジルコニウム（ＺｒＯ２）を含む原料を下記の表２に示す組成となるように秤量したこと以外は、比較例１と同様にして固体電解質層を作製し、上記の方法でイオン伝導度を測定した。結果を表２に示す。 (Example 4)
As raw materials, lithium hydroxide monohydrate (LiOH.H 2 O), gallium oxide (Ga 2 O 3 ), aluminum oxide (Al 2 O 3 ), lanthanum hydroxide (La (OH) 3 ), zirconium oxide ( A solid electrolyte layer was prepared in the same manner as in Comparative Example 1 except that the raw material containing ZrO 2 ) was weighed so as to have the composition shown in Table 2 below, and the ionic conductivity was measured by the above method. The results are shown in Table 2.
　（実施例５）
　原料として、水酸化リチウム一水和物（ＬｉＯＨ・Ｈ２Ｏ）、酸化ガリウム（Ｇａ２Ｏ３）、酸化アルミニウム（Ａｌ２Ｏ３）、水酸化ランタン（Ｌａ（ＯＨ）３）、酸化ジルコニウム（ＺｒＯ２）を含む原料を下記の表２に示す組成となるように秤量したこと以外は、比較例１と同様にして固体電解質層を作製し、上記の方法でイオン伝導度を測定した。結果を表２に示す。 (Example 5)
As raw materials, lithium hydroxide monohydrate (LiOH.H 2 O), gallium oxide (Ga 2 O 3 ), aluminum oxide (Al 2 O 3 ), lanthanum hydroxide (La (OH) 3 ), zirconium oxide ( A solid electrolyte layer was prepared in the same manner as in Comparative Example 1 except that the raw material containing ZrO 2 ) was weighed so as to have the composition shown in Table 2 below, and the ionic conductivity was measured by the above method. The results are shown in Table 2.
　（実施例６）
　原料として、水酸化リチウム一水和物（ＬｉＯＨ・Ｈ２Ｏ）、酸化ガリウム（Ｇａ２Ｏ３）、酸化アルミニウム（Ａｌ２Ｏ３）、水酸化ランタン（Ｌａ（ＯＨ）３）、酸化ジルコニウム（ＺｒＯ２）を含む原料を下記の表２に示す組成となるように秤量したこと以外は、比較例１と同様にして固体電解質層を作製し、上記の方法でイオン伝導度を測定した。結果を表２に示す。 (Example 6)
As raw materials, lithium hydroxide monohydrate (LiOH.H 2 O), gallium oxide (Ga 2 O 3 ), aluminum oxide (Al 2 O 3 ), lanthanum hydroxide (La (OH) 3 ), zirconium oxide ( A solid electrolyte layer was prepared in the same manner as in Comparative Example 1 except that the raw material containing ZrO 2 ) was weighed so as to have the composition shown in Table 2 below, and the ionic conductivity was measured by the above method. The results are shown in Table 2.
Figure JPOXMLDOC01-appb-T000002
 　表２に示す結果から、ＧａとＡｌとの含有量の総量を一定として、Ｇａの含有量とＡｌの含有量とを変化させた場合のイオン伝導度の変化が分かる。表２に示す結果から、Ａｌの含有量をＬａの含有量に対して０．６６モル％より多くすることでイオン伝導度を大きく向上できることが分かる。また、Ｇａの量がＬａの含有量に対し、０．６７モル％より少なくなることで伝導度が減少することが分かる。従って、Ｇａの含有量は０．６６モル％より多いことが好ましい。Ａｌに対するＧａの含有比が０．１より多く１より少ない領域において、伝導度がほぼ極大となり、より好ましいことがわかる。
Figure JPOXMLDOC01-appb-T000002
 From the results shown in Table 2, it can be seen that the ionic conductivity changes when the total content of Ga and Al is constant and the Ga content and the Al content are changed. From the results shown in Table 2, it can be seen that the ionic conductivity can be greatly improved by increasing the Al content to more than 0.66 mol% with respect to the La content. It can also be seen that the conductivity decreases when the Ga content is less than 0.67 mol% with respect to the La content. Accordingly, the Ga content is preferably more than 0.66 mol%. It can be seen that in the region where the content ratio of Ga to Al is more than 0.1 and less than 1, the conductivity becomes almost maximum, which is more preferable.
　（実施例７）
　原料として、水酸化リチウム一水和物（ＬｉＯＨ・Ｈ２Ｏ）、酸化ガリウム（Ｇａ２Ｏ３）、酸化アルミニウム（Ａｌ２Ｏ３）、水酸化ランタン（Ｌａ（ＯＨ）３）、酸化ジルコニウム（ＺｒＯ２）を含む原料を下記の表３に示す組成となるように秤量したこと以外は、比較例１と同様にして固体電解質層を作製し、上記の方法でイオン伝導度を測定した。結果を表３に示す。 (Example 7)
As raw materials, lithium hydroxide monohydrate (LiOH.H 2 O), gallium oxide (Ga 2 O 3 ), aluminum oxide (Al 2 O 3 ), lanthanum hydroxide (La (OH) 3 ), zirconium oxide ( A solid electrolyte layer was produced in the same manner as in Comparative Example 1 except that the raw materials containing ZrO 2 ) were weighed so as to have the composition shown in Table 3 below, and the ionic conductivity was measured by the above method. The results are shown in Table 3.
　（実施例８）
　原料として、水酸化リチウム一水和物（ＬｉＯＨ・Ｈ２Ｏ）、酸化ガリウム（Ｇａ２Ｏ３）、酸化アルミニウム（Ａｌ２Ｏ３）、水酸化ランタン（Ｌａ（ＯＨ）３）、酸化ジルコニウム（ＺｒＯ２）を含む原料を下記の表３に示す組成となるように秤量したこと以外は、比較例１と同様にして固体電解質層を作製し、上記の方法でイオン伝導度を測定した。結果を表３に示す。 (Example 8)
As raw materials, lithium hydroxide monohydrate (LiOH.H 2 O), gallium oxide (Ga 2 O 3 ), aluminum oxide (Al 2 O 3 ), lanthanum hydroxide (La (OH) 3 ), zirconium oxide ( A solid electrolyte layer was produced in the same manner as in Comparative Example 1 except that the raw materials containing ZrO 2 ) were weighed so as to have the composition shown in Table 3 below, and the ionic conductivity was measured by the above method. The results are shown in Table 3.
　（実施例９）
　原料として、水酸化リチウム一水和物（ＬｉＯＨ・Ｈ２Ｏ）、酸化ガリウム（Ｇａ２Ｏ３）、酸化アルミニウム（Ａｌ２Ｏ３）、水酸化ランタン（Ｌａ（ＯＨ）３）、酸化ジルコニウム（ＺｒＯ２）を含む原料を下記の表３に示す組成となるように秤量したこと以外は、比較例１と同様にして固体電解質層を作製し、上記の方法でイオン伝導度を測定した。結果を表３に示す。 Example 9
As raw materials, lithium hydroxide monohydrate (LiOH.H 2 O), gallium oxide (Ga 2 O 3 ), aluminum oxide (Al 2 O 3 ), lanthanum hydroxide (La (OH) 3 ), zirconium oxide ( A solid electrolyte layer was produced in the same manner as in Comparative Example 1 except that the raw materials containing ZrO 2 ) were weighed so as to have the composition shown in Table 3 below, and the ionic conductivity was measured by the above method. The results are shown in Table 3.
　（実施例１０）
　原料として、水酸化リチウム一水和物（ＬｉＯＨ・Ｈ２Ｏ）、酸化ガリウム（Ｇａ２Ｏ３）、酸化アルミニウム（Ａｌ２Ｏ３）、水酸化ランタン（Ｌａ（ＯＨ）３）、酸化ジルコニウム（ＺｒＯ２）を含む原料を下記の表３に示す組成となるように秤量したこと以外は、比較例１と同様にして固体電解質層を作製し、上記の方法でイオン伝導度を測定した。結果を表３に示す。 (Example 10)
As raw materials, lithium hydroxide monohydrate (LiOH.H 2 O), gallium oxide (Ga 2 O 3 ), aluminum oxide (Al 2 O 3 ), lanthanum hydroxide (La (OH) 3 ), zirconium oxide ( A solid electrolyte layer was produced in the same manner as in Comparative Example 1 except that the raw materials containing ZrO 2 ) were weighed so as to have the composition shown in Table 3 below, and the ionic conductivity was measured by the above method. The results are shown in Table 3.
Figure JPOXMLDOC01-appb-T000003
 　表３に示す結果から、Ｇａ：Ａｌを、大凡１：３として、ＧａとＡｌとの含有量の総量を変化させた場合のイオン伝導度の変化が分かる。表３に示す結果から、Ｌｉの含有量が６．１より多く６．６よりも少ない場合（すなわち、０．４＜３ｘ＋ａｙ＜０．９）に高いイオン伝導度が得られることが分かる。０．６＜３ｘ＋ａｙ＜０．９のときにより高いイオン伝導度が得られることが分かる。
Figure JPOXMLDOC01-appb-T000003
 From the results shown in Table 3, the change in ionic conductivity when Ga: Al is approximately 1: 3 and the total content of Ga and Al is changed can be seen. From the results shown in Table 3, it can be seen that high ionic conductivity is obtained when the Li content is more than 6.1 and less than 6.6 (that is, 0.4 <3x + ay <0.9). It can be seen that higher ionic conductivity is obtained when 0.6 <3x + ay <0.9.
１　全固体電池
１１　正極
１２　負極
１３　固体電解質層 
 
  DESCRIPTION OF SYMBOLS 1 All-solid-state battery 11 Positive electrode 12 Negative electrode 13 Solid electrolyte layer

Claims (7)

  1. 　ガーネット型の結晶構造を有する固体電解質であって、
    　Ｌｉ，Ｌａ，Ｚｒ，Ｏ及びＧａと、
    　Ａｌ，Ｍｇ，Ｚｎ及びＳｃからなる群から選ばれた少なくとも１種の元素と、
    　を含む、固体電解質。     A solid electrolyte having a garnet-type crystal structure,
    Li, La, Zr, O and Ga;
    At least one element selected from the group consisting of Al, Mg, Zn and Sc;
    Including a solid electrolyte.
  2. 　Ｇａの含有量が、Ｌａの含有量に対して０モル％よりも多く１３．４モル％より少なく、
    　Ａｌ，Ｍｇ，Ｚｎ及びＳｃからなる群から選ばれた少なくとも１種の元素の含有量の合計が、Ｌａの含有量に対して０モル％よりも多く１３．４モル％より少なく、
    　Ｇａの含有量と、Ａｌ，Ｍｇ，Ｚｎ及びＳｃからなる群から選ばれた少なくとも１種の元素の含有量との合計が０．３０モル％より多く２０モル％より少ない、請求項１に記載の固体電解質。     Ga content is more than 0 mol% and less than 13.4 mol% with respect to La content,
    The total content of at least one element selected from the group consisting of Al, Mg, Zn and Sc is greater than 0 mol% and less than 13.4 mol% with respect to the La content;
    The sum of the Ga content and the content of at least one element selected from the group consisting of Al, Mg, Zn and Sc is more than 0.30 mol% and less than 20 mol%. Solid electrolyte.
  3. 　Ｇａの含有量が、Ｌａの含有量に対して０．６６モル％よりも多く６．６７モル％より少なく、
    　Ａｌ，Ｍｇ，Ｚｎ及びＳｃからなる群から選ばれた少なくとも１種の元素の含有量の合計が、Ｌａの含有量に対して０モル％よりも多く６．６７モル％より少なく、
    　Ｇａの含有量と、Ａｌ，Ｍｇ，Ｚｎ及びＳｃからなる群から選ばれた少なくとも１種の元素の含有量との合計が０．３３モル％より多く１０モル％より少ない、請求項２に記載の固体電解質。     Ga content is more than 0.66 mol% and less than 6.67 mol% with respect to La content,
    The total content of at least one element selected from the group consisting of Al, Mg, Zn and Sc is greater than 0 mol% and less than 6.67 mol% with respect to the La content;
    The sum of the Ga content and the content of at least one element selected from the group consisting of Al, Mg, Zn, and Sc is greater than 0.33 mol% and less than 10 mol%. Solid electrolyte.
  4. 　Ｚｒの含有量が、Ｌａの含有量に対して５０モル％以上８０モル％以下であり、
    　Ｌｉの含有量が、Ｌａの含有量に対して１９７モル％以上２８０モル％以下である、請求項１～３のいずれか一項に記載の固体電解質。     The Zr content is 50 mol% or more and 80 mol% or less with respect to the La content,
    The solid electrolyte according to any one of claims 1 to 3, wherein the Li content is 197 mol% or more and 280 mol% or less with respect to the La content.
  5. 　一般式（Ｌｉ７－（３ｘ＋ａｙ）ＧａｘＭｙ）Ｌａ３Ｚｒ２Ｏ１２（Ｍは、Ａｌ，Ｍｇ，Ｚｎ及びＳｃからなる群から選ばれた少なくとも１種の元素であり、ａはＭの価数であり、０＜ｘ＜０．３、０＜ｙ＜０．３、０．４＜３ｘ＋ａｙ＜０．９）で表される、請求項１～４のいずれか一項に記載の固体電解質。 General formula (Li 7- (3x + ay) Ga x M y ) La 3 Zr 2 O 12 (M is at least one element selected from the group consisting of Al, Mg, Zn and Sc; The solid according to any one of claims 1 to 4, which is a valence and is represented by 0 <x <0.3, 0 <y <0.3, 0.4 <3x + ay <0.9). Electrolytes.
  6. 　一般式（Ｌｉ７－（３ｘ＋３ｙ）ＧａｘＭｙ）Ｌａ３Ｚｒ２Ｏ１２（ＭはＡｌであり、０＜ｘ＜０．３、０＜ｙ＜０．３、０．１＜ｘ／ｙ＜１、０．６＜３ｘ＋３ｙ＜０．９）で表される、請求項５に記載の固体電解質。 General formula (Li 7- (3x + 3y) Ga x M y ) La 3 Zr 2 O 12 (M is Al, 0 <x <0.3, 0 <y <0.3, 0.1 <x / y The solid electrolyte according to claim 5, represented by <1, 0.6 <3x + 3y <0.9).
  7. 　請求項１～６のいずれか一項に記載の固体電解質を含む固体電解質層と、
    　前記固体電解質層の一方面に焼結によって接合されている正極と、
    　前記固体電解質層の他方面に焼結によって接合されている負極と、
    　を備える、全固体電池。 
          A solid electrolyte layer comprising the solid electrolyte according to any one of claims 1 to 6;
    A positive electrode joined by sintering to one side of the solid electrolyte layer;
    A negative electrode joined by sintering to the other surface of the solid electrolyte layer;
    An all solid state battery.
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